CN109589931A - A kind of magnetism covalent organic framework compound solid phase extraction adsorbents and preparation method - Google Patents
A kind of magnetism covalent organic framework compound solid phase extraction adsorbents and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of magnetic covalent organic framework compound magnetic solid phase extraction adsorbent and preparation methods, belong to analytical chemistry and technical field of food safety detection.The present invention provides a kind of magnetic covalent organic framework compound solid phase extraction adsorbents and preparation method thereof, utilizes N Atomic coordinate in Fe ion and TpBD, the COF- obtained using coprecipitation method (TpBD)/Fe3O4Mixture is as adsorbent, for extracting, purifying the aromatic compound in food substrate, especially phthalate object.The method of the present invention simplifies the process of sample pre-treatments, simple and quick to be easy to get using Co deposited synthesis magnetic adsorbent, reduces extraction workload, and the method for the present invention substantially reduces the detection limit of phthalate compound.
Description
Technical field
The present invention relates to a kind of magnetic covalent organic framework compound magnetic solid phase extraction adsorbent and preparation method, belong to point
Analysis chemistry and technical field of food safety detection.
Background technique
Magnetic solid phases extract (MSPE) adsorbent and rapid dispersion can adsorb in sample solution, can be fast using external magnets
Speed separation.Compared with conventional solid extracts (SPE), MSPE has many clear advantages, including easy to operate, reduces organic molten
The consumption of agent, avoid SPE filler it is tightly packed caused by high back pressure and quick and easy external magnet separation analyte,
It is easy to the advantages that being combined with detecting instrument.The important component of MSPE is adsorbent material, it determines the sensitivity of this method
And selectivity.Therefore exploitation has the Magnetic solid phases of adsorption effect to extract (MSPE) adsorbent PAEs, and absorption property can be improved.
Covalent organic framework (COF) is a kind of novel crystallization porous material with higher order structures, by organic building
Unit is constituted.COF has many unique properties, such as permanent porosity and bigger serface, this leads COF in chromatography
Great potentiality are shown in domain.However its lower density disperses its form often extremely, affects its application.Cause
This, it is magnetized, can be in conjunction with the advantages of MSPE, to promote the practical application of COF.Has nucleocapsid structure at present
COF@Fe3O4Report of the material as magnetic solid phase extraction adsorbent, but synthesis process needs strict control, limits the wide of material
General application.For example, reported Fe3O4@TpBD nucleocapsid structure magnetic covalently-organic backbone nanosphere needs to be added orthosilicic acid tetrem
Ester (TEOS) and (3- aminopropyl) triethoxysilane (APTES) are to introduce amino, then growth in situ TpBD, whole process
Need strict control；The Fe of no amino modified dose of participation3O4@COF- (TpBD) nuclear shell structured nano ball still needs strict control
Synthesis process, to guarantee preferable crystalline structure.
There is the pore size of the pi-conjugated system of π-, rigidity based on COF material TpBDThe spies such as chemistry, thermal stability
Point, we are applied to the extractive analysis of the object with aromatic structure.In view of phthalic acid ester (PAEs) chemistry
Structure and molecular dimension are (about), using the size selection effect of itself and TpBD, π-is pi-conjugated and hydrophobic forces, I
Studied by taking the PAEs in food as an example.Phthalic acid ester is often used as plasticizer to increase the flexibility of plastics,
The transparency, durability and service life.Since its potential carcinogenicity and possible endocrine metabolic diseases act on, it is considered to be have hair
Educate the endocrine disruption chemical substance of toxicity.Since PAEs is not chemically combined with plastic substrate, it is easy under certain conditions
It is transferred in food from food plastic packaging material, so the problem of food pollution of PAEs has become public attention.Currently, being permitted
Multinational family has all formulated the Limited Doses of phthalic acid ester.Ministry of Health of China general office is clearly stipulate that phthalate object
Matter must not contact grease based food and infant food, the phthalic acid two (α-ethylhexyl ester) in food, food additives
(DEHP), diisononyl phthalate (DINP) and n-butyl phthalate (DBP) maximum residue limit are respectively
1.5mg/kg, 9.0mg/kg and 0.3mg/kg.In recent years, PAEs causes more and more to pay close attention to the pollution of food.Therefore it opens
Hair detect the simplicity of phthalic acid ester in various samples quickly, environmental protection, practical approach very it is necessary to.
Summary of the invention
In order to solve problem above, the present invention provides a kind of magnetic covalent organic framework compound solid phase extraction adsorbents
And preparation method thereof, and it is applied to the magnetic solid phase extraction of phthalic acid ester.The present invention passes through co-precipitation and Electrostatic Absorption
Method quickly and easily synthesizing new magnetic solid phase extraction adsorbent, it is bigger serface, porosity based on COF material, big
The characteristics of pi-conjugated system of π-and thermal stability, the adsorbent have significant enrichment to aromatic compound.Currently, will
The method of COF material magnetization is mostly to synthesize the nano material of nucleocapsid structure, and synthesis process needs strict control.Therefore, one is invented
Kind quickly and easily COFs is magnetized and method that enrichment aromatic compound can be efficiently separated be emphasis of the invention it
One.Present invention can apply to the direct magnetic solid phase extractions of more complex matrix, can allow gas-chromatography or liquid chromatographic detection.
The first purpose of the invention is to provide a kind of preparation method of New Magnetic Field Controlled solid phase extraction adsorbents, the method is
Co-precipitation is implemented in combination with using COF-TpBD and Fe ion coordination key, comprising: COF-TpBD, iron ion source are placed in water, added
Then ammonium hydroxide is added to 30~80 DEG C in heat, isolated COF- (TpBD)/Fe after fully reacting3O4Magnetic solid phase extraction adsorbent.
In one embodiment of the present invention, the finger mass ratio of the COF- (TpBD) and iron ion source is (0.04
~0.12): 1, the iron ion source includes ferrous ion source and ferric ion.
In one embodiment of the present invention, the mass ratio of the ferrous ion source and ferric ion is 1:(1.5
~3).
In one embodiment of the present invention, the volume ratio of the ammonium hydroxide and aqueous solution is 3%~10%.
In one embodiment of the present invention, the mass ratio of the COF-TpBD and iron ion source be (0.04~
0.12): 1.
In one embodiment of the present invention, the COF-TpBD has high-crystallinity, extended system, chemical stability
It is good.
In one embodiment of the present invention, the synthetic method of the COF-TpBD is raw in situ including the use of solvent-thermal method
The methods of regular way, ionothermal synthesis, microwave-assisted solvent thermal method, heating reflux method, solution at room temperature method are realized.
In one embodiment of the present invention, the method is coprecipitation, wherein COF- (TpBD) and Fe3O4It is coprecipitated
The mechanism in shallow lake is with Fe ion (having unoccupied orbital) using the N atom (with lone pair electrons) in COF- (TpBD) with coordinate bond
In conjunction with.
In one embodiment of the present invention, the ferrous ion source includes its hydrochloride, sulfate, in nitrate
It is one or more.
In one embodiment of the present invention, the ferric ion source includes its hydrochloride, sulfate, in nitrate
It is one or more.
In one embodiment of the present invention, the method specifically includes:
(1) by COF-TpBD, FeSO4·7H2O and FeCl3·6H2O is mixed with 150mL water, and is passed through nitrogen；
(2) mixed solution is stirred evenly, and is heated to 30~80 DEG C, 4.5~15mL ammonium hydroxide is added, and continue stirring 30
~40min；
(3) after above-mentioned solution is cooling, the material of synthesis is collected using external magnet, and successively using deionized water and
Ethanol washing material, drying for standby.
In one embodiment of the present invention, the COF-TpBD is to utilize solvent structure, and use acetone, four
Hydrogen furans, ethanol washing, are dried to obtain.
A second object of the present invention is to provide a kind of New Magnetic Field Controlled solid phase extraction adsorbents COF- (TpBD)/Fe3O4。
Third object of the present invention is to provide a kind of extraction or the method for separating aromatic compound, the method packets
It includes and utilizes above-mentioned magnetic solid phase extraction adsorbent.
In one embodiment of the present invention, which comprises
(1) according to mass volume ratio, by COF- (TpBD)/Fe3O4It is molten to be added to 10~100mL determinand by 10~40mg
In liquid, and by solution vortex oscillation 15~50 minutes；
(2) magnetic collection COF- (TpBD)/Fe3O4, and twice with pure water；
(3) methanol or acetonitrile is then added, elutes COF- (TpBD)/Fe3O4On object；
(4) use external magnet by COF- (TpBD)/Fe3O4It is adsorbed on chamber wall, collects supernatant to get aromatic series
Compound solution.
The extraction or isolated principle are as follows: COF- (TpBD)/Fe3O4In COF- (TpBD) and object between lead to
One or more of selection effect, π-πconjugation and the hydrophobic forces for crossing pore size are adsorbed.
Fourth object of the present invention is to provide a kind of detection method of aromatic compound, and the method is to treat in advance
It surveys object progress pre-treatment and obtains sample, then gained sample is detected；The pre-treatment is extracted using above-mentioned magnetic solid phase
Adsorbent is taken to carry out.
In one embodiment of the present invention, the detection includes that gas-chromatography or gas chromatography-mass spectrum device join
With.
In one embodiment of the present invention, the aromatic compound is with benzene ring structure and double bond conjugated structure
Aromatic compound of the molecular weight less than 1000 dalton, the alkyl including C10~C20, or have aryl, ester, ether, amine,
The compound of the alkyl of the groups such as amide or the hydrophobic mass such as the alkyl of double bond or ester group.
Fifth object of the present invention is to provide a kind of extracting process of phthalate compound, the method packets
It includes:
(1) by above-mentioned magnetic solid phase extraction adsorbent COF- (TpBD)/Fe3O4, salt is added in determinand solution and mixed
Solution is closed, is adsorbed；
(2) COF- (TpBD)/Fe is taken out3O4, methanol or acetonitrile is added and carries out elution parsing, be separated off COF- (TpBD)/
Fe3O4To get phthalic acid ester PAEs solution.
In one embodiment of the present invention, COF- (TpBD)/Fe3O4Mass volume ratio with determinand solution is (10
~40): (10~100) mg/mL.
In one embodiment of the present invention, salinity is 0.5%~1.5%w/v in step (1).
In one embodiment of the present invention, the adsorption time in step (1) is 5~45min.
In one embodiment of the present invention, step (2) 2~25min of elution time.
In one embodiment of the present invention, the pH value of mixed solution is 5.0~8.0 in step (1).
Sixth object of the present invention is to provide a kind of detection method of aromatic compound, the method is to treat in advance
It surveys object progress pre-treatment and obtains sample, then gained sample is detected；The pre-treatment is to utilize above-mentioned extracting process
It carries out.
Compared with prior art, remarkable advantage is the present invention:
(1) preparation method of magnetic adsorbent of the present invention is easy to be quick, and the solvent stability of resulting magnetic adsorbent is good,
Reusable 5 times or more；
(2) extraction separating method of aromatic compound of the present invention solves above compound tradition method for separating and concentrating and easily makes
At cross contamination, the problem of using a large amount of organic solvents, the present invention is without the use of a large amount of organic solvents and vessel, fully demonstrates
Its environmental-friendly feature；
(3) detection method of aromatic compound of the present invention simplifies the process of sample pre-treatments, easy to operate, reduces work
It measures, and testing result is preferable, the detection limit and quantitative limit of a variety of PAEs is all lower.
Detailed description of the invention
Fig. 1 is COF-TpBD and synthesis Fe3O4The optimization of the feed ratio of the raw material of equivalent；
Fig. 2 is TpBD, Fe3O4、COF-(TpBD)/Fe3O4X-ray diffraction (XRD) figure；
Fig. 3 is Fe3O4With COF- (TpBD)/Fe3O4B-H loop；
Fig. 4 is TpBD, Fe3O4、COF-(TpBD)/Fe3O4Fourier transform infrared spectroscopy (FT-IR) figure；
Fig. 5 is the type optimization figure of extractant；
Fig. 6 is the optimization figure of extractant volume；
Fig. 7 is the dosage optimization figure of magnetic adsorbent；
Fig. 8 is the optimization figure of different solutions sample volume；
Fig. 9 is the optimization figure of extraction time；
Figure 10 is the optimization figure of elution time；
Figure 11 is the optimization figure of salt ionic concentration；
Figure 12 is the optimization figure of pH value.
Specific embodiment
In conjunction with example, the invention will be further described:
Embodiment 1: magnetic solid phase extraction adsorbent of the preparation based on COF material
(1) stable covalent organic framework compound material the preparation of COF material: is generated by solvent thermal reaction.It selects
COF material be COF-TpBD, synthesize it is raw materials used be respectively three aldehyde radical phloroglucin (Tp) 63mg (0.3mmol), benzidine
(BD)48mg(0.45mmol).Synthesizing organic solution used is mesitylene 3mL, and Isosorbide-5-Nitrae-dioxane 3mL, catalyst is 6M second
Acid solution 0.3mL.By above-mentioned material ultrasonic mixing it is uniform after be transferred to Teflon reaction kettle, 120 DEG C are reacted 72 hours.Material takes
It is washed, and is dried in vacuo spare repeatedly with acetone out.
(2) magnetization of COF material: Co deposited synthesis COF- (TpBD)/Fe is used3O4.Take ferric chloride hexahydrate
(FeCl3·6H2O) 0.4g, green vitriol (FeSO4·7H2O the COF-TpBD 35mg after) 0.25g, with appropriate grinding
In a round bottom flask, and 100mL pure water is added.It is stirred evenly at 60 DEG C using Teflon stirring rod, and 9mL ammonium hydroxide is added,
It is heated to 80 DEG C to continue to stir 30min, then cool to room temperature.Using pure water resulting materials 2~3 times, second is then used
Alcohol washs 2~3 times, drying for standby in a vacuum drying oven.
The characterization of magnetic solid phase extraction adsorbent:
The TpBD, Fe prepared by XRD characterization3O4With COF- (TpBD)/Fe3O4Crystal structure and purity.As shown in Fig. 2,
TpBD, COF- (TpBD)/Fe of synthesis3O4XRD lab diagram and simulation it is consistent, show the successful preparation of TpBD and smooth magnetic
Change.Fe3O4With COF- (TpBD)/Fe3O4B-H loop it is as shown in Figure 3.Fe3O4With COF- (TpBD)/Fe3O4Saturated magnetization
Intensity value is respectively 61.1 and 51.8.Fe3O4With COF- (TpBD)/Fe3O4Relatively high saturation magnetization makes this suction
Attached dose easily affected by magnetic fields, easily separates with solution system.
COF- (TpBD)/Fe is confirmed by FT-IR spectrum3O4The chemical composition and structure (Fig. 4) of nano material.With COF-
(TpBD) spectrum is compared, COF- (TpBD)/Fe3O4Spectrum in 584cm-1Place shows additional absorption band, this is attributed to
The Fe-O-Fe of magnetic iron ore vibrates.For COF- (TpBD), 1442cm-1The signal at place represents the feature tension belt of aromatics C=C key,
C-N stretches and the characteristic peak of C=N key is respectively in 1292 and 1605cm-1, this is because having in the synthetic reaction of TpBD from enol form
Thaumatropy is the process of ketone form structure.
Embodiment 2:
Referring to embodiment 1, the present invention is using single factor experiment to COF-TpBD and synthesis Fe3O4Source of iron raw material feed intake
It is investigated than optimizing, as shown in Figure 1, feed ratio has more influence to the extraction absorption property of material, in mass ratio
0.04:1 dosage below, adsorption effect is generally poor, is no more than 10%, 0.04:1 or more, absorption property is gradually promoted, and is being reached
When to 0.12:1, the adsorption effect of multiple compounds is up to 100%.
Embodiment 3: COF- (TpBD)/Fe is used3O4Extraction and detection to 15 kinds of PAEs in drink sample
(1) titer is prepared: concentration is the PAEs- methanol standard solution of 1000mg/mL, including DMP/DEP/DIBP/
DBP/DMEP/BMPP/DEEP/DPP/DHXP/BBP/DBEP/DCHP/DEHP/DphP/DNOP gradient dilution to 100mg/mL,
10mg/mL, respectively as storage liquid and intermediate fluid.Standard curve working solution concentration is 5 μ g/mL, 10 μ g/mL, 20 μ g/mL, 50 μ
G/mL, 100 μ g/mL, 200 μ g/mL, 500 μ g/mL, 1000 μ g/mL, matching while using.
(2) pre-treatment of sample to be tested
Beer, soda and alcohol carbonated beverage deaerate in ultrasonic bath, eliminate carbon dioxide.Then, matrix
More complex beverage such as milk drink, fruit juice and milk tea pure water are with the dilution proportion of 1:8, and Other Drinks pure water is with 1:5's
Dilution proportion, to reduce matrix interference before extraction process.
(3) PAEs background is eliminated
Since PAEs is widely available in many Lab Products, including chemicals and glassware, therefore in practical sample
There may be high backgrounds in the analysis of PAEs in product.To avoid PAEs from polluting, all glassware application acetone used or just
Hexane washing, and using preceding at least 4h dry at 120 DEG C.All organic solvents used in analysis experiment are chromatographically pure
Grade.The organic solvent and plastic product that those are unavoidably used should be analyzed by GC-MS first, with eliminate PAEs pollution can
It can property.
(4) Magnetic solid phases extract
Specific steps are as follows: 1) material 30mg COF- (the TpBD)/Fe prepared in Example 13O4, it is added to 50mL mark-on
In solution or sample solution.2) by after solution vortex oscillation, using strong magnets by COF- (TpBD)/Fe3O4It collects, and with pure
Water washing is twice.3) it is then desorbed using 2mL methanol, and vibrates elution COF- (TpBD)/Fe3O4On object.4) make
With external magnet by COF- (TpBD)/Fe3O4Be adsorbed on chamber wall, collect all supernatants and by the filtering of 0.22 μm of film with
Particulate matter is removed before CG analysis, is analyzed using GC.Used COF- (TpBD)/Fe3O4It is washed three times, is returned with methanol
It receives and utilizes.
(1) this experiment is detected using gas chromatography-mass spectrography.Detection pattern is more reaction detections (MRM) mode.
Chromatogram is recorded, Software Integration is carried through chromatograph and obtains peak area, draw 15 kinds of phthalic acid ester standard curves, and calculate
Obtain the content of each phthalic acid ester in sample to be tested.
The measurement of each phthalic acid ester in 1 sample to be tested of table
Embodiment 4:
Investigation is optimized to extraction conditions in this experiment: referring to the condition in embodiment 1, it is real to make single factor test optimization respectively
It tests.
Test two kinds of eluting solvents (acetonitrile and methanol), provided with different effluent volume (0.5mL × 2,1mL,
1mL × 2,2mL), the amount (10,20,30,40mg) of magnetic adsorbent, different sample solution volumes (10mL, 50mL, 100mL,
200mL), extraction time (5,10,20,30,40,45min), elution time (2,5,10,15,20,25min), salt ionic concentration
(0,0.3,0.5,1,1.5%w/v) and pH value (5.0,5.5,6.0,6.5,7.0,7.5,8.0).As Fig. 5, Fig. 6, Fig. 7, Fig. 8,
Shown in Fig. 9, Figure 10, Figure 11, Figure 12, have finally chosen the preferable extraction conditions of effect of extracting: 2mL methanol as eluting solvent,
30mg COF-(TpBD)/Fe3O4As adsorbent, 30min is used as elution time as extraction time, 15 minutes, and salt ion is dense
Degree is 1%w/v, pH value 7.0.
Claims (10)
1. a kind of preparation method of magnetic solid phase extraction adsorbent, which is characterized in that the method is to utilize covalent organic framework
It closes the N atom in object COF-TpBD with lone pair electrons and is implemented in combination with co-precipitation with the Fe ion coordination key with unoccupied orbital, wrap
It includes: COF-TpBD, iron ion source is placed in water, be heated to 30~80 DEG C, ammonium hydroxide is then added, is separated after fully reacting to obtain the final product
COF-(TpBD)/Fe3O4Magnetic solid phase extraction adsorbent.
2. the method according to claim 1, wherein the mass ratio of the COF-TpBD and iron ion source is
(0.04~0.2): 1.
3. method according to claim 1 or 2, which is characterized in that the iron ion source includes ferrous ion and trivalent
Iron ion, wherein the mass ratio of ferrous ion and ferric ion is 1:(1.5~3).
4. the method according to claim 1, wherein the COF- (TpBD)/Fe3O4Magnetic solid phase extraction adsorbent
In the material with adsorption effect be TpBD, using the pi-conjugated absorption of the selection effect of pore size, π-and it is one of hydrophobic or
Several active forces, adsorb object.
5. a kind of magnetic solid phase extraction adsorbent, which is characterized in that the magnetic solid phase extraction adsorbent is to utilize Claims 1 to 44
What any the method was prepared.
6. a kind of method of extraction or separating aromatic compound, which is characterized in that the method is to utilize claim 5 institute
The magnetic solid phase extraction adsorbent stated, comprising:
(1) according to mass volume ratio, by COF- (TpBD)/Fe3O410~40mg is added in 10~100mL determinand solution,
It mixes；
(2) COF- (TpBD)/Fe is collected3O4, washing；
(3) solvent is then added, elutes COF- (TpBD)/Fe3O4On aromatic compound object；
(4) it is separated off COF- (TpBD)/Fe3O4, clear liquid is collected to get aromatic compound solution.
7. a kind of extracting process of phthalate compound, which is characterized in that the described method includes:
(1) by magnetic solid phase extraction adsorbent COF- (TpBD)/Fe described in claim 53O4, 0.5%~1.5%w/v salt be added
Mixed solution is obtained into determinand solution, is adsorbed；
(2) COF- (TpBD)/Fe is taken out in separation3O4, methanol or acetonitrile is added and carries out elution parsing, be separated off COF- (TpBD)/
Fe3O4To get phthalic acid ester PAEs solution.
8. the method according to the description of claim 7 is characterized in that COF- (TpBD)/Fe3O4With the mass body of determinand solution
Product is than being (10~40): (10~100) mg/mL.
9. method according to claim 7 or 8, which is characterized in that the pH value of mixed solution is 5.0 in the step (1)
~8.0.
10. a kind of detection method of aromatic compound, which is characterized in that the method is to carry out pre-treatment to determinand in advance
Sample is obtained, then gained sample is detected；The pre-treatment is adsorbed using magnetic solid phase extraction described in claim 5
Agent, or carried out using any extraction separating method of claim 6~9.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110133125A (en) * | 2019-05-07 | 2019-08-16 | 曲阜师范大学 | A kind of method that Magnetic solid phases extraction detects plant growth regulator in fruits and vegetables |
| CN110152632A (en) * | 2019-05-27 | 2019-08-23 | 浙江省农业科学院 | A kind of magnetic COF-TpPa and its preparation method and application for being enriched with amides pesticide |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107413313A (en) * | 2017-07-18 | 2017-12-01 | 武汉大学 | A kind of Magnetic solid phases extractant based on covalent organic framework material and its preparation method and application |
| CN108262019A (en) * | 2018-02-11 | 2018-07-10 | 中国烟草总公司郑州烟草研究院 | A kind of magnetism sulfonic functional COFs materials and its preparation method and application |
| CN108355613A (en) * | 2018-03-02 | 2018-08-03 | 南京师范大学常州创新发展研究院 | Magnetic covalent organic framework material and its preparation method and application |
-
2018
- 2018-12-05 CN CN201811480471.1A patent/CN109589931B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107413313A (en) * | 2017-07-18 | 2017-12-01 | 武汉大学 | A kind of Magnetic solid phases extractant based on covalent organic framework material and its preparation method and application |
| CN108262019A (en) * | 2018-02-11 | 2018-07-10 | 中国烟草总公司郑州烟草研究院 | A kind of magnetism sulfonic functional COFs materials and its preparation method and application |
| CN108355613A (en) * | 2018-03-02 | 2018-08-03 | 南京师范大学常州创新发展研究院 | Magnetic covalent organic framework material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| GUO LIN, ET AL.: "Room-temperature synthesis of core–shell structured magnetic covalent organic frameworks for efficient enrichment of peptides and simultaneous exclusion of proteins", 《CHEM. COMMUN.》 * |
| SIJING HE, ET AL.: "Facile Synthesis of Magnetic Covalent Organic Framework with Three-Dimensional Bouquet-Like Structure for Enhanced Extraction of Organic Targets", 《ACS APPL. MATER. INTERFACES》 * |
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